Insecticidal composition



Patented Jan. 4, 1944 UNITED STATES QPA'IIFENT orncr:

assasso msnc'rrcman COMPOSITION William F. Hester, Drexel Hill, and W E Craig;

Philadelphia, Pa., asslgnors to Riilun & Haas Company, Philadelphi Delaware No Drawing a, Pa., a corporation of Application November 28, 1940, Serial No. 367,569

9 Claims, (01. 187-40) This invention relates to insecticidal compositions having as an active principle a compound of the iormula COR (Noah-MN CHxCHaZ wherein Ar is an aryl nucleus of the-benzene or naphthalene series, Z is a member of the class consisting of H, -'OR, and OCOR, and n is an integer having a value from one to two inclusive, R representing a hydrocarbon group from the aliphatic, aromatic, or alicyclic series, such as methyl, ethyl, allyl, propyl, isopropyl, butyl, methallyl, octyl, undecenyl, dodecyl, octadecenyl, octadecyl, benzyl phenyl, methyl phenyl, naphthyl, napthenyl, abietyl, etc.

Compounds of the above type may be prepared by various known procedures, such as the reaction of a nitrochlorobenzene or'nitrobromonaphthalene with ethanolamine in the presence of an alkali, and conversion oi. the resulting ethanolic compound to an ether or ester. In some cases a nitroaniline may be reacted with an ether haiide or ester 01' a halohydrin, such as phenoxyethyl chloride, ethoxyethyl chloride, or the acetate o! chlorohydrin to yield compounds of the for- I mula (N01) --ArI ICH|CH 0 R and Compounds of this type may be acylated to in-' troduce on the amine nitrogen a -COR group in place of the hydrogen.

To illustrate the preparation of typical compounds, the iollowing examples are given.

' Example 1 A mixture of 157.5 parts of o-nitrochlorobenzene, 61 parts of ethanolamine, and 212 parts of soda ash was stirred-and heated under reflux for ethanola-mine, 60 parts of water, and parts of sodium hyroxide was stirred and heated under reflux for one hour, whereupon the mixture was cooled, filtered, and concentrated. The product recrystallized from alcohol, melts at 87-88" C. and has the composition I ammonimhnncmmon I Example 3 (a) 36 parts of the product from Example 1,- 100 parts of glacial acetic acid, 22 parts of acetic anhydride, and a trace oi concentrated sulfuric acid were mixed and refluxed ior'two hours. The reaction mixture was cooled and poured into ice water, with the formation of a'solid, which was separated by filtration, washed with water, and crystallized from alcohol to give 36 parts of a solid melting at til-62 C. and corresponding to (b) Another 36 parts of, product from Example 1 was reacted with 100 parts of. glacial acetic acid, parts 01' aceticanhydride, and a small amount of sulfuric acid under reflux for five hours, and then treated as above, The solid obtained, amounting to 30 parts, melted at 64- 65 C. When mixed crystals from So above, a mixed melting point of 45-50" C. was obtained. The product corresponds in composition to secticidal agent in an organic solvent and apply 8 hours, and thereafter steam distilled, leaving v a tarry residue, which was taken up in hot benzene. On cooling, parts of crystals were obtained, having a melting point of 73'74 C., an corresponding to the formula 2-NO2CBH4NHCH2CH2OH V Example 2 A mixture of 200 parts of 2,4-dlnitrochlorobenzene. 980 parts of '95%-ethanol, 60 parts of .it in this form or in'the form of an emulsion by adding a suitable emulsifying agent, such as a sulionated oil.- I

' A useful spray of the latter type may be prepared by dissolving one part of the toxicant with one partof emulsifying agent in two parts of pine oil and extending this preparation with to 400 parts of water. This gives an effective concentration of toxicant 01 one part in 400 to one part in 1600.

Various compounds were spread on finely divided solids by dissolving the compounds in inert solvents, mixing the solution with the solid, and evaporating the solvent while the mixture was stirred. The compounds may also be spread on solids by mixing the toxicant with a solid or fusing a toxicant with an inert solid and grinding the mixture. A spray containing one part of active agent, two parts. of magnesium carbonate, one-half part of a condensed sulfonated alkyl phenoxyethanol sulfate as a spreader, and 96.5 parts of water was applied to bean plants. Twenty-four hours later Mexican bean beetle larvae were applied to the plants and after a'second twenty-four hours" observation was made of the eifect of the toxicant on the larvae, counts being made of the insects which had fallen fromqthef' plant, dead or no longer capable of feeding on it. Results were'as follows:

Compound Control 2,4-(Nz) 2CsH3N (COCHa) CHaCHzOCOCHa- 99 Similar results were obtained by applying the .toxicants in dusts, which were also prepared by spreading the active agent at concentrations of to on a finely divided solid. Typical formulae for dusts are:

Parts A. Toxicant 1 Talc 98 Spreader 1 B. Toxicant 1 Alum sludge 48 Lime 48 Soya bean oil 3 COR (N na- N CHzCHaZ wherein Ar is an aryl nucleus selected from a member of the benzene and naphthalene series, Z is a member of the class consisting of OH, OR, and OCOR groups, and n is an integer having a value from one to two inclusive, R being a hydrocarbon group selected from the aliphatic, aromatic, and alicyclic series.

2. An insecticidal composition containing as an active principle a compound of the formula (NOalr-Phenyk-N CHzCHrZ wherein Z is a member of the class consisting of OH, OR, and OCOR groups, R being a hydrocarbongroup selected from the aliphatic. aromatic, and alicyclic series.

3. An insecticidal composition comprising as an active principle a compound of the formula wherein Z is a member of the class consisting of OH, OR, and OCOR groups, B being a hydrocarbon group selected from the aliphatic, aromatic, and alicyclic series. 4. An insecticidal composition containing as an active principle a compound of the formula C O R 01) -phenyi-N CEsCHsO C 0 R wherein n is an integer from one to two inclusive, and R is a hydrocarbon radical selected from the aliphatic, aromatic, and alicyclic series. 5

5. An insecticidal composition containing as an active principle a compound of the formula (NOzhCcHtN CHSCHlO 0 0R wherein R is an alkyl group.

6. An insecticidal composition containing as an active principle a compound of the formula Z is a member of the class consisting of OR, OR, and OCOR groups, n is an integer having a value from one to two, inclusive, and R is a hydrocarbon group selected from the aliphatic, aromatic, and alicyclic series, said active ingredient being dispersed in an aqueous emulsion.

8. A process of controlling soft-bodied insects on living plants which comprises spraying plants infested with said insects with an aqueous emulsion containing in dispersed form a compound of the formula 1 COR.

CHzCHrZ wherein Ar is an aryl nucleus selected from a member of the benzene and naphthalene series, Z is a member of the class consisting of OH, OR, and OCOR groups, n is an integer having a value from one to two, inclusive, and R is a hydrocarbon group selected from the aliphatic, aromatic, and alicyclic series.

9. A process of controlling soft-bodied insects on living plants which comprises spraying plants infested with said insects with an aqueous emulsion containing in dispersed form a compound of the formula 'NomoanN omonio 00 on.

WILLIAM F. HESTER. W E CRAIG. 

